The only other change to the team that started in Parma sees Sean Doyle preferred at openside flanker, with Mike McComish moving to the replacements bench.
Payne starts at full-back alongside Andrew Trimble and Craig Gilroy in the back-three. Darren Cave and Luke Marshall continue in midfield with Pienaar partnering Paddy Jackson at half-back.
The game will be particularly significant for young Ireland international Jackson as it is his 50th senior outing for Ulster.
South African Muller returns in the second row alongside Dan Tuohy, with Doyle, Roger Wilson and Robbie Diack making up the back row.
The Ulstermen are top of Pool 5 having beaten Leicester Tigers and Montpellier. Saturday's round 3 game is live on Sky Sports 2 interactive (red button) and on BBC Radio Ulster (Medium wave).
ULSTER (v Benetton Treviso): Jared Payne; Andrew Trimble, Darren Cave. Luke Marshall, Craig Gilroy; Paddy Jackson, Ruan Pienaar; Tom Court, Rob Herring, John Afoa, Johann Muller (capt), Dan Tuohy, Robbie Diack, Sean Doyle, Roger Wilson.
Replacements: Niall Annett, Callum Black, Declan Fitzpatrick, Neil McComb, Mike McComish, Paul Marshall, Michael Allen, David McIlwaine.